Process for preparing hexadienes from conjugated diolefinic hydrocarbons and alpha-monoolefins



United States Patent PROCESS FOR PREPARING HEXADIENES FROM CONJUGATED DIOLEFINIC HY- DROCARBONS AND a-MONOOLEFINS Masao Iwamoto and Sadao Yuguchi, Ohtsu-shi, Japan, assignors to Toyo Rayon Kabushiki Kaisha, Tokyo, Japan, a corporation of Japan No Drawing. Filed Oct. 7, 1965, Ser. No. 493,914

'Claims priority, application Japan, Oct. 9, 1964, 39/57,334; Oct. 22, 1964, 39/59,697; Dec. 10, 1964, 39/69,146; Dec. 29, 1964, 39/7 1,567; Jan. 8, 1965, 40/615; Jan. 21, 1965, 40/2,768; Mar. 5, 1965, 40/12,363, 40/12,366; Mar. 22, 1965, 40/16,297; Apr. 8, 1965, 40/20,284

11 Claims. (Cl. 260-680) ABSTRACT OF THE DISCLOSURE A method of producing hexadienes by the reaction of an a-monoolefin with a conjugated diolefin in the presence of a three-component catalyst comprising (1) a salt of cobalt or iron, (2) a tertiary phosphine or an oxide thereof wherein said phosphine has two phosphorus atoms and (3) an organoaluminum compound.

This invention relates to a process for preparing hexadienes..More particularly, the invention relates to a process for preparing hexadienes in good yield by reacting alpha-olefins with conjugated diolefinic hydrocarbons in the presence of a new catalyst composition consisting of a certain compound of cobalt or iron, a certain organophosphorus compound and an organoaluminum compound.

The hexadienes are compounds having various valuable uses as intermediates. Recently, the 1,4-hexadienes have been attracting attention particularly as the third component for imparting sulfur vulcanizability to the ethylcue-propylene copolymer, the so-called ethylene-propylene rubber.

It has been known to prepare 1,4-hexadienes by reacting ethylene with 1,3-butadiene in the presence of prescribed catalysts. For example, US. Patent 3,152,195 discloses a process wherein rhodium chloride is used as the catalysts. On the other hand, French patent specification 1,388,305 discloses a process wherein a combination of a nickel-phosphorus complex and an organometallic compound is used as the catalyst.

However, the rhodium chloride which is used as the catalyst in the former process is very costly. Hence the production cost inevitably rises when this compound is used. On the other hand, in the latter process the selectivity for the intended hexadienes is not satisfactory.

It is therefore an object of the present invention to provide a process for obtaining the intended hexadienes in good yield and with high selectivity by reacting alphaolefins with conjugated diolefinic hydrocarbons in the presence of a new catalyst of low cost.

Another object of this invention is to provide a new catalyst composition which not only is inexpensive but whose activity is exceedingly great.

Other objects and advantages of the present invention will become apparent from the following description.

The foregoing objects are attained by a process for preparing hexadienes in accordance with the present invention, which comprises reacting an alpha-olefin with a conjugated diolefinic hydrocarbon in the presence of a catalytic amount of a three-component composition comprising:

(1) (a) a compound of the formula M(C H O where M is cobalt or iron, and n is an integer equal to the valence of said metal; or

(b) a compound of the formula MX where X is halogen and M and n have the meanings defined above;

(2) an organophosphorus compound having either the formula R P--R where R is either alkyl or aryl, R is alkylene, alkenylene or arylene group, and n is an integer either 0 or 1; and (3) an organoaluminum compound having the formula where R" is a monovalent hydrocarbon radical,Z is either hydrogen or halogen, and m is a numeral from 1 to 3.

Of the iron or cobalt compounds that are used as the first component of the catalyst in the present invention, the acetylacetonate complex having the formula As the halogenide of the formula MX included are the chlorides such as Fecl FeCl CoCl and C00,, the bromides such as FeBr FeBr CoBr and CoBr and the iodides such as FeI- Fel CoI and CoI Of the foregoing compounds, particularly preferred in the invention process are the trivalent iron compounds, i.e. FeCl FeBr and Fe(C H O the divalent halogenides of cobalt, i.e. CoCl and CoBr and the acetyl acetonate complexes of cobalt, i.e. CO(C5H702)2 and Co(C H-;O

The aforesaid tertiary diphosphines having the formula R P{-R'},,PR which are used as the second component of the catalyst in the present invention, are exemplified by 1,1-bis(diphenylphosphino) methane, 1,2 bis(diphenylphosphino)ethane, 1,2 bis(diethylphosphino) ethane, 1,2 bis(diphenylphosphino)ethylene, 1,3 bis(diphenylphosphino) propane, 1,4 bis(diphenylphosphino)butane, 1,5 bis(diphenylphosphino) benzene, tetramethyl biphosphine and tetraethyl biphosphine.

In general, when m is 1 in the foregoing formula, R is preferably a phenyl group, while R is preferably an alkylene group of 1-4 carbon atoms, or a phenylene group. Of these, it is particularly preferred where R is a phenyl group and R is a propylene or ethylene group.

On the other hand, when n is 0, it is preferred that the aforesaid R is an alkyl group of 1-4 carbon atoms. Thus, of the foregoing compounds, conveniently usable are the 1,2 bis(diphenylphosphino)ethane, 1,3- or 1,2-bis(diphenylphosphino)ethane, 1,3- or 1,2-bis(diphenylphosphino)propane, 1,2-bis(diphenylphosphino)ethylene, 1,2- bis(dihenylphosphino)benzene and tetraethyl bisphosphine.

On the other hand, the phosphoryl derivative represented by the formula 1,2-bis(diphenylphosphoryl)ethane, 1,3-bis(diphenylphosphoryl)propane, 1,4 bis(diphenylphoshoryl)butane, 1,2- bis(dihenylphosphoryl)benzene and tetraethyl diphosphoryl.

In the foregoing formula, it is generally preferred that R' is an alkylene group of 1-4 carbon atoms and R is a phenyl group. Thus, of the foregoing compounds, those usable with particular convenience are the l,2-bis(diphenylphosphoryl)ethane and 1,3 bis(diphenylphosphoryl propane.

On the other hand, the aforesaid organoaluminum compounds of the formula R AlZ the third component of the catalyst, are preferably those in which the R is an alkyl group, and particularly a lower alkyl group. Examples of these compounds include the trialkylaluminums such as triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, and triisobutylaluminum, the dialkylaluminum monohalides such as diethylaluminum monochloride, diethylaluminurn monobromide, diethylaluminum monoiodide, diisobutylaluminum monochloride and diisobutylaluminum monobromide, the alkylaluminum dihalides such as ethylaluminum dichloride, ethylaluminum dibromide, isobutylaluminum dichloride, isobutylaluminum dibromide and isobutyl aluminum diiodide, the alkylaluminum sesquihalides such as ethylaluminum sesquichloride, ethylaluminum sesquibromide, isobutylaluminum sesquibromide and hexlyaluminum sesquichloride, and the alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride. These compounds can be used alone or as a mixture.

Of the foregoing compounds, the trialkylaluminums, dialkylaluminum monohalides and alkylaluminum sequihalides are easily available and can generally be used with convenience in this invention.

Although the optimum molar ratio condition of the aforesaid three components to be added to make up the catalyst in the process of the present invention will differ somewhat in accordance with the specific compounds chosen for said components, generally speaking, good results can usually be obtained when the molar ratio of the organophosphorus compound to the cobalt or iron compound (P/Metal) is 0.111 to 5:1, preferably 0.521 to 2:1 and that of the organoaluminum compound to the cobalt or iron compound (Al/Metal) is 0.5 :1 to 200:1, preferably 5:1 to 100:1.

These catalyst components either may be added directly to the reaction system or the three components may be prepared as a mixture in advance to their addition to the system. In the instance particularly when the cobalt or iron halide of the formula MX,, is used as the first component of the catalyst, exceedingly good results are obtained by reacting the halide with the organophosphorus compound, the second component, to form a complex of either the formula [MX [R P -R'-},,PR or the formula where the proportion of x to y is 1:1 or 1:2, and this is used in combination with the organoaluminum compound.

Examples of particularly suitable combinations of the foregoing catalyst components include:

In the process of the present invention, alpha-olefins are reacted with conjugated diolefinic hydrocarbons in the presence of a catalytic amount of the foregoing threecomponent catalyst.

The alpha-olefins, which are used in the present invention as the starting material, are those hydrocarbons of the formula RCH=CH where R is hydrogen or an alkyl group of 1-8 carbon atoms. Included, for example, are ethylene, propylene, butene-l, pentene-l, hexene-l and heptene-l, particularly preferred being ethylene and propylene.

The conjugated diolefinic hydrocarbons, which are used in this invention as the other starting material, are either 1,3-butadiene or the alkyl or aryl-substituted 1,3-butadienes. Of these compounds, those suitably used in the invention process are 1,3-butadiene and the 2-alkyl-1,3-butadienes, 4-alkyl-1,3-butadienes, 2,3-dialkyl-l,3-butadienes, 1,4 dialkyl 1,3-butadiene and 2,4-dialkyl-l,Z-butadiene (the alkyl groups here indicated are those of 1-20 carbon atoms, and preferably 16 carbon atoms). Thus, as typical compounds can be mentioned 1,3-butadiene, isoprene, 2- ethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4- hexadiene, 2,3 dimethyl 1,3 butadiene, 2,3-diethyl-1,3- butadiene and 2-methyl-1,3-pentadiene. Moreover, as arylsubstituted-l,S-butadiene, 2-phenyl-l,3-butadiene may be used. Generally, the use of 1,3-butadiene' and isoprene is to be preferred.

The alpha-olefins and conjugated diolefinic hydrocarbons are reacted stoichiometrically of course, but it not necessarily required that these reactants are present in the reaction system in equivalent quantities. For example, the reaction may be made to proceed by merely introducing the alpha-olefin into the reaction system, in the case where the total amount of the conjugated diolefinic hydrocarbon has been added to the system in advance.

The amount of the catalyst used relative to these starting materials will vary depending upon the particular catalyst system used but, generally speaking, it is usually preferred that the cobalt or iron salt be present in an amount of 10 to 10 moles, and particularly 10- to 10 moles to every one mol of the conjugated diolefinic hydrocarbon.

In those instances where the conjugated diolefinic hydrocarbon is liquified in the reaction system, the use of a solvent may be dispensed with. However, for minimizing as much as possible the occurrence of a reaction between the conjugated diolefinic hydrocarbon and enhancing the amount formed of the intended hexadienes, it is preferred to use a suitable solvent, consideration being given to the dispersibility and solubility of the catalyst.

Conveniently usable as such a solvent are the hydrocarbons such as pentane, heptane, cyclohexane, benzene, toluene and xylene and the halogenated hydrocarbons such as chlorobenzene, bromobenzene, methylene chloride, 1,2-dieh1oroethane and 1,3-diehloropropane. Further, if a substance which is gaseous at room temperature such as propane and butane is used as the solvent, the separation of the solvent by means of distillation is made much more easy.

On the other hand, it was found that when the intended hexadiene was hexadiene-1,4 the selectivity for hexadiene-l,4 was enhanced still more when the reaction Was carried out in the presence of a halogenated hydrocarbon. Furthermore, since these solvents dissolve the aforementioned cobalt complex completely, there was also the advantage that the handling of the catalyst was made easier.

According to the present invention, there are no particular restrictions as to the reaction temperature and pressure as well as the other reaction conditions, variation of these conditions over a broad range being possi- I le.

A reaction temperature ranging between l0 and 250 C. is convenient, a range between 10 and C. being especially desirable. On the other hand, the reaction pressure may be either normal atmospheric or superatmospheric. In general, a pressure of 5-300 kg. per square centimeter is conveniently used depending upon the alpha-olefin used.

Thus the desired hexadienes can be synthesized by the invention process by suitably varying the conditions within the ranges indicated hereinabove. For example, when ethylene is used as the alpha-olefin, the relationship vbetween the class of the conjugated diolefinic hydrocarbon used and the resulting hexadienes are, in general, as follows.

(1 1,3-butadiene- 1,4-hexadiene, 2,4-hexadiene,

1,3-hexadiene.

(2) 2-alky1-1,3-'butadiene 5-alkyl-1,4-hexadiene, 4-alkyl-1,4-hexadiene, 2-alkyl-2,4-hexadiene, 3-alkyl-2,4-hexadiene (3 4-alkyl-l,3-butadiene 3-alkyl-1,4-hexadiene, 6-alkyl-1,4-hexadiene, 3-alky1-2,4-hexadiene, 6-alkyl-2,4-hexadiene (4) 2,3-dialkyl-1,3 butadiene 4,5-dia1kyl-1,4-

hexadiene, 2,3-dialkyl-2,4-hexadiene (5) 1,4-dialkyl-1,3-butadiene 4,6-dialkyl-1,4-

hexadiene, 3,5-dialkyl-l,4-hexadiene (6) 2-pheny1-l,3-butadiene+4-phenyl-1,4-hexadiene On the other hand, when propylene is used as the alpha-olefin, the hexadiene obtained is as follows:

butadiene-e 2-met'hy1- 1,4-hexadiene and 2-methyl-1,3-hexadiene.

Further, as the conjugate diolefinic hydrocarbon it is also possible to use, for example, the hexadiene-2,4 obtained by isomerization of hexadiene-1,4. Thus, according to this invention, such hexadienes can also be reacted further with ethylene.

The proportion with which the products are obtained from the same starting materials can be varied over a broad range by means of the choice and combination of the catalyst components, the choice of solvent as previously noted, and changes in the reaction conditions.

The critical feature of the present invention resides in the point that a catalyst composition containing a specific organophosphorus compound, i.e. a tertiary phosphine or tertiary phosphoryl, is used. In consequence of the use of such a catalyst system, the formation of by-products as a result of the dimerization or polymerization of the conjugated diolefinic hydrocarbon is extremely small, and the yield (seeictivity) or hexadiene per diolefin reacted becomes as much as 85 to 97%. Thus the selectivity for the intended hexadiene also becomes very high. For example, when preparing hexadiene-1,4 from butadiene-1,3, the selectivity for hexadiene-l,4 becomes as high as 85-95%, a value markedly superior to the less than 70% that was generally attained by the conventional methods.

According to the present invention, it is possible to provide, as hereinbefore described, a broad range of hexadienes on a commercial scale, using a low-cost catalyst. The so obtained hexadienes, for example, hexadiene-l,4, are useful without further treatment as monomers for polymerization or copolymerization in the plastic, rubber, textile and adhesive fields. In addition, they are also important as intermediates of those valuable compounds having two functional groups.

For a clear understanding of the present invention, the following examples are given. Unless otherwise indicated, the percentages are on a weight 'basis.

Example 1 0.19 gram of a dark green crystalline complex of the formula CoCl (C H PCH CH P(C H 2 obtained by mixing anhydrous cobalt chloride CoCl with 1,2- bis (diphenylphosphino)ethane in molar ratio 1:2 was charged to 50 cc. of monochlorobenzene in a 200-cc. autoclave along with 1 cc. of triethylaluminum as catalyst, after which 34.2 grams of butadiene were also added.

This mixture was then reacted by maintaining a constant ethylene pressure of 20 kg./cm. One hour later, 45.4 grams of hexadiene-1,4 and 4.7 grams of hexadiene-2,4 were obtained. The yield of hexadienes reached an amount 98% of theory.

Example 2 gram Of CoCl [(C H PCH CH P(C H prepared as described in Example 1, was charged to 50 cc. of toluene in an autoclave along with 1 cc. of triethyaluminum, followed by the addition also of 67 grams of butadiene. The reaction was then carried out for 55 minutes by maintaining an ethylene pressure at 70 C. of 20 kg./cm. 82 grams of hexadienes were obtained and the reaction rate of the butadiene was Examples 3-5 The reactions were carried out for 2 hours at an ethylene pressure of 50 l g./cm. using 50 cc. of toluene and 1 cc. of AlEt in all instances but, as the tertiary diphosphine complex, 0.1 millimol of C0Bl'2(Ph2P(CH2)2PPh )2 in Examples 3 and 4 and 0.1 millimol of in Example 5. The amounts of butadiene used in Examples 3, 4 and 5 were respectively 43.5, 33.5 and 36.8 grams. The results obtained are tabulated below.

TABLE I Example Butadiene, g. Tempeature, Hexadiene, g.

As is apparent from the foregoing table, when CoI (Ph P (CH PPh 2 is present as the catalyst, not only is the activity high but the selectivity for formation of hexadiene-1,4 is also equally as good as in the instance of the use of a chloride complex.

Example 6 A magnetic rotary agitator equipped 200-cc. autoclave was charged with 20 cc. of toluene 0.08 gram of CoCl (Ph PCH CH PPh (also referred to as Co complex hereinafter), 33.5 grams of liquified butadiene, and 2 cc. of triisobutylaluminum in the order given,

following which the autoclave was sealed and the reac-' Example 7 Two cc. of diisobutylalurninum hydride (100%) was used instead of the triisobutylaluminum of Example 6. After operating as in Example 6, 15.8 grams of hexadiene-1,4 and 1.1 grams of hexadiene-2,4 were obtained. The selectivity for hexadiene-l,4 was 88.5%.

Example 8 A rotary agitator-equipped 20'0-cc. autoclave was charged with 0.5 millimoles of anhydrous cobalt chloride and 20 cc. of toluene. This was followed by the addition of 1 rnillimole of 1,2-bis(diphenylphosphino)ethane, 67 grams of liquified butadiene and 1 cc. (about 7.3 millimols) of trimethylaluminum, in the order given, after The procedures described in Example 8 were followed, except that instead of the anhydrous cobalt chloride 0.5 millimole of a hexahydrate of cobalt chloride was added, followed by the addition of 0.5 gram of 1,2-bis(diphenylphosphino)ethane. After carrying out the reaction for 4 hours using 33.5 grams of butadiene and an ethylene pressure of 35 kg./cm. 31 grams of hexdadienes were obtained. The conversion of the butadiene was 67%, and the proportion of hexadiene-1,4 in the hexadienes was 93%. The selectivity for hexadiene-1,4 was 85.6%.

Examples -12 Except that the catalyst concentration, molar ratio of diphosphine to cobalt compound, the molar ratio of aluminum to cobalt, the ethylene pressure and reaction periods used were those shown in Table H, below, otherwise the procedures as described in Example 8 were followed with the results shown in said Table II.

8 Example This example, along with Examples'16 and 17, shows how important the matter of selection of the solvent is.

When 0.09 gram of a cobalt complex was added to 4 cc. of ethylene chloride, a dark green solution was obtained. When after adding 50 cc. of toluene to this solution and also 33.5 grams of butadiene and 0.55 cc. of AlEt the reaction was carried out for 2 hours at a temperature of 80-90 C. and an ethylene pressure of 54.5 kg./cm. 38.6 grams of hexadiene-1,4, 2.2 grams of hexadiene-2,4 and 1.3 grams of other products were obtained.

On the other hand, when toluene was not added as the solvent and 67 grams of butadiene and 1 cc. of AlEt were used, 59.6 grams of hexadiene-l,4, 16.5 grams of hexadiene-2,4 and 18.6 grams of a C diolefins were obtained, and isomerization of the hexadiene took place at a high rate. C diolefin is a compound obtained by the reaction of ethylene with hexadiene-2,4.

Example 16 When 0.09 gram of CoCl [Ph PCH CH PPH was dissolved in 50 cc. of tetrachloroethylene to which was then added 1 cc. of AlEt and 36.2 grams of butadiene and the reaction was carried out for 2 hours at a temperature of 97.99 C. while maintaining the pressure at kg./cm. with ethylene, 57.3 grams of hexadiene-l,4 and 3.1 grams of hexadiene-2,4 were obtained. The conversion of the butadiene was practically 100%.

TABLE II 00012, PhzPCHZCHzPPhz, Ethylene Hexadiene HD1,4 HD-1 ,4 g. HD/g. P/Co, Al/Co, Example mmole mrnole Pressure, Time, hr. (HD), g. in HD, Selectivity, (Co-l-P) molar molar kg./cm. percent percent ratio ratio Example 13 Example 17 A 200-cc. autoclave equipped with a magnetic rotary agitator was charged with 0.09 gram of CDC/12 )2 cc. of toluene, 34.8 grams of liquified butadiene and 0.55 cc. of AlEt in the order given, following which the autoclave was sealed. The reaction was carried out for 2 hours, adjusting the ethylene pressure to become 40 kg./cm. at 140 C. Then by treating the reaction product in customary manner, 41.79 grams of hexadiene-2,4 were obtained. The amount of hexadiene-1,4 was 16.5 grams. Besides this, 6.79 grams of other distillation residues were obtained.

Example 14 The reaction was carried out following the procedures described in Example 13, except that 1.08 cc. of the AlEt were used and the temperature during the first one hour was maintained at 130140 C. while the temperature during the second one hour was raised to 168170 C. Of the product obtained, hexadiene-2,4 amounted to 52.7 grams and hexadiene-1,4 to 1.2 grams, while conjugated dienes made up 96.5% of the hexadienes. Besides this, there was also observed a slight formation of hexadiene-1,3.

When 50 cc. of ethylene chloride, 33.5 grams of butadiene, 0.09 gram of a cobalt complex and 0.5 cc. of AlEt were reacted for 2 hours at C. with an ethylene pressure of 40 kg./cm. 38.3 grams of a diene of a molecular weight 110 (C H composed of 1 butadiene molecule and 2 ethylene molecules were obtained. This was composed of two components, namely, 3-methylheptadiene-l,4 and 3-ethylhexadiene-1,4.

Examples 18-23 A. By reacting in liquid ammonia NaP(C H synthesized from metallic sodium and triphenylphosphine, with 1,3-dichloropropane, 1,3-bis(diphenylphosphino) propane was obtained as a white powder (M.P. 61- 62 C.).

When foregoing diphosphine dissolved in toluene was mixed with anhydrous cobalt chloride suspended, in ethanol, a blue precipitate was obtained (M.P. 230- 233 C.).

B. A 300-cc. autoclave was charged with 20 cc. of toluene, following which the CoCl [Ph P(CH PPh prepared as hereinabove described, butadiene and trialkylaluminum were added as indicated in Table III, below. The reactions were then carried out at a temperature of 80-90" C. and an ethylene pressure of 50 kg./cm. with the results shown below in Table III.

TABLE III Cobalt Butadiene, Hexadiene-1,4 Hexadiene-2,4, Others, Residue, Reaction Example Complex AlRa, cc. g. g. g. g. g. Time, hr.

(male) 0. 5 AlEta, 0.7 20. 5 13. 4 20.8 5 3.1 19 0. 5 AlEta, 0.7 20.5 24. 4 2. 3 1. 5 4 1 0. 5 AlEta, 0.2 105. 8 0 18. 4 5.8 2.0 (1.25 11115153, 1.5.- 100 116.7 0 10.3 2.1 3 0.125 AlEta, 1.5 100 51.8 0 4.1 2.2 3 0.25 AlMca, 1.5. 114 101.8 0 11.1 4. 8 3

In Example 23, about 2.5 kg. or more of hexadiene-1,4 can be formed per gram of the cobalt complex.

Example 24 A rotary agitator-equipped 200-cc. autoclave was charged with 0.1 gram of the cobalt complex of Example 18, dissolved in ethylene chloride. Then, after adding 1.16 cc. of AlEt and 85.7 grams of butadiene, the reaction was carried out for 2 hours at 98-102 C. while maintaining a pressure of 38 kg./cm. with ethylene to yield 67.2 grams of hexadiene-1,4, 8.7 gram of 3-methy1- heptatriene (3-MHT) and 2.8 grams of other products.

Examples 25-26 TABLE IV 10 AlEt and the reaction was carried out for 19 hours at 80 C. by charging ethylene to a pressure of 50 kg./cm. 15.9 grams of a product of the following composition were obtained: 44.8% hexadiene-1,4, 17.8% hexadiene- 2,4, 2.8% cyclohexene and 34.6% high boiling substances.

Example 31 A magnetic rotary agitator-equipped autoclave was first charged with 20 cc. of toluene, after which complex obtained from one millimole of 1,2-bis(diphenylphosphoryl) ethane i and 0.5 millimole of anhydrous cobalt chloride was added. Then, after adding 47 grams of butadiene and 1 cc. of AlEt the autoclave was sealed followed by introduction of ethylene under pressure so as to maintain a pressure of 50 kg./cm. at 80-90 C.

When the reaction was carried out for 3 hours with stirring, 90.5 grams of hexadiene-1,4 were obtained. The amount of hexadiene-2,4 by isomerization was 2.1 grams,

C0012, 1,3 bis(dipheny1- Tempera- Time, Hexadiene-1,4, Hexadiene-2,4, Others, Example mmole phosphino)propane, ture, 0. hr. g. g. g.

mmole Example 27 and that of the atmospheric distillation residue was 1.45

The apparatus described in Example 18 was used, which was charged with 5 cc. of ethylene chloride, 0.125 millimole of cobalt chloride, 0.125 millimole of the diphosphine of *Example 18 and 67 grams of butadiene, and 0.83 gr. AlEt in the order given. When the reaction was then carried out for 3 hours at 80-90 C. under an ethylene pressure of 60 kg./cm. 83.7 grams of hexadiene-1,4, 0.64 gram of 3-MHT and 1.7 grams of atmospheric distillation residue were obtained. It was confirmed the hexadiene-l,4 was obtained at the rate of 1,285 grams per gram of the cobalt and phosphine compound combined.

Example 28 A 100-cc. autoclave was charged with 20 cc. of toluene, 0.5 millimole of CoCl 0.84 millimol of 20.5 grams of butadiene and 5.11 millimoles of A1Et When the reaction was then carried out for 17 hours at 80 C. by charging ethylene to a pressure of 50 kg./cm. 28.4 grams of a product containing the following components were obtained, the proportion of which were 74.5% hexadiene-l,4, 6.2% hexadiene-1,3, 0.3% hexadiene-2,4, 1.7% cyclohexene, 9.6% 3-methylheptatriene- 1,4,6, 3.7% n-octatriene-1,3,6, 1% vinyl cyclohexene and 6.9% high boiling substances.

Example 29 When a 100cc. autoclave was charged with 20 cc. of toluene, 0.5 millimole of CoCl 0.74 millimol of Et PPEt 30 cc. of butadiene and 10.95 millimoles of AlEt and the reaction was carried out for 19 hours at 80 C. by charging ethylene to a pressure of 50 kg./crn. 26.9 grams of a product of the following composition were obtained: 6 6.4% heXadiene-1,4, 17% hexadiene- 2,4, 9.1% cyclohexene and 7.5% high boiling substances.

Example 30 When a 100-cc. autoclave was charged with 20 cc. of toluene, 0.5 millimole of CoCl 0.84 millimole of Et P-PEt 30 cc. of butadiene and 21.9 millimoles of grams. The conversion of the butadiene was 94.4%.

Example 32 Except that as the diphosphoryl t tum om wtmn was used, the reaction was otherwise carried out as in Example 31 to yield 12 grams of hexadienes. In this case, 27.4 grams of the dimers of butadiene was produced as a by-product.

Example 33 One hundred cc. of B-B fraction containing 30% by volume of butadiene (50% by volume of isobutylene and 20% by rvolume of other C; isomers) and ethylene were reacted in the following manner. To an autoclave containing 20 cc. of toluene was added 0.09 gram of C0012 s s 2 2 2 s s 2] 2 dissolved in 10 cc. of ethylene chloride. Then, the foregoing B-B fraction and 1 cc. of Al(C H were also charged to the autoclave, following which ethylene was introduced up to a pressure of 50 kg./cm. (1 00102 C.) and the reaction was carried out for 2 hours.

After releasing the pressure, the product was given an extraction treatment with water containing a small amount of hydrochloric acid. When the organic layer was dried and the components were separated by gas chromatographic and distillation treatments, 21.1 grams of hexadiene-1,4, 2.4 grams of hexadiene-2,4 and 0.6 gram of C dienes were obtained. The residue by atmospheric distillation amounted to about 1 gram. Products resulting from the reaction between isobutylene and ethylene and between isobutylene and butadiene were not obtained. The conversion of butadiene as calculated from the product was 84.2%.

Example 34 As in Example 33, the catalyst, solvent and reaction gases were charged into a magnetic rotary agitatorequipped 200-cc. autoclave. As the reaction gases, cc. of a B-B fraction containing 50% by volume of butadiene (40% by volume of butene-l and 10% by volume of other C, isomers) under pressure and ethylene under a pressure of 50 kg./cm. were introduced.

When the reaction was carried out and the product treated as in Example 33, 31.6 grams of hexadiene-1,4, 2.06 grams of hexadiene-2,4 and 0.63 gram of atmospheric distillation residue were obtained. The conversion of the butadiene was 86 .3%.

Example 35 The same procedures as described in Example 33 were followed, except that 1 cc. of the B-B fraction used was one which Was condensed and collected from the cylinder, then regasified and again condensed by passing through a dry tube. As a result, 58.5 grams of hexadiene- 1,4 were obtained.

Example 36 Twenty cc. of toluene, 0.08 gram of Coclz s )2 2 2 s 5) 212 33.5 grams of liquified butadiene, 30.5 grams of liquified propylene and 1 cc. of (C H Al were charged to a 200- cc. autoclave, in the order given, following which the reaction was carried out for 16.5 hours at 100 C. From the gas chromatograph of the product, two by-products close to the main product can be observed.

It was confirmed from various tests that this main product was 2-methyl hexadiene-1,4. This product amounted to 5.1 grams.

Example 37 A magnetic rotary agitator-equipped 200cc. autoclave was charged with 40 cc. of toluene, 0.25 millimole of CoCl 0.5 millimole of a cis type 36.2 grams of butadiene and 1.03 cc. of (C H Al, following which the autoclave was sealed. The reaction was then carried out for 2 hours at 94-100 C. by introducing ethylene up to a pressure of 50 kg/cm. and maintaining this pressure during the reaction to yield 50.3 grams of hexadiene-l,4 and 2 grams of hexadiene- 2,4 at a conversion for the butadiene of 98%. The atmospheric distillation residue amounted to 0.56 gram.

Example 38 Instead of the cis type in Example 37, a trans type (C H PCH=CHP(C H was used. After a reaction for 2 hours at 102-106 C., 19.7 grams of hexadiene-1,4 and 2.1 grams of hexadiene-2,4 were obtained. Besides these, 4 grams of dimers of butadiene were obtained. The atmospheric distillation residue amounted to 0.63 gram and the conversion of the butadiene was 57.3%.

Example 39 A 100-cc. autoclave replaced with ethylene gas was charged with 0.356 gram (1 millimole) of cobalt (I11) acetyl acetonate, 1,212 grams (2.2 millimole) of 1,2-bis (diphenylphosphino)ethane, 20 cc. of ethane and 2 cc. of diethylaluminum chloride and then stirred for 15 minutes at room temperature. Next, 32.4 grams (0.6 mole) of liquid butadiene were charged to the autoclave by means of distillation. The temperature was maintained at 50 C., the pressure was brought up to l g./cm. with ethylene, and stirring was continued for 2 hours. After cooling of the autoclave, the residual ethylene gas was discharged, and the catalyst was decomposed with dilute hydrochloric acid. As a result of this reaction, 42.5 grams of hexadiene-1,4 and 0.3 gram of hexadiene- 2,4 were obtained. The high boiling distillation residue amounted to 1.4 grams.

Examples 40-46 A 100-cc. autoclave was charged with 0.178 gram (0.5 millimole) of cobalt (III) acetyl acetonate, 0.275

gram (0.5 millimole) of 1,2-'bis(diphenylphosphino) ethane, 20 cc. of toluene and 1 cc. of diethylaluminum chloride, and the mixture was stirred for 15 minutes at room temperature. Then the autoclave was charged with 16.2 grams (0.3 mole) of butadiene, followed by stirring for 25 minutes at C. under an ethylene pressure of 40 kg./cm. to yield 23.6 grams of hexadiene-1,4 and 0.4 gram of hexadiene-2,4. The yield of hexadienes was 77% of theory.

Reactions were carried out using 0.5 millimole of the below-listed diphosphines instead of the 1,2-bis(diphenylphosphin0)ethane, the other conditions being the same. The results obtained are shown in Table V, below.

TABLE V Hexa- Hexa- Example Tertiary diphosphine dieuediene 41 1,l-bis(diphenylphosphino)methane... 12.1 1. 2 42 1,2-bis(diphenylphosphino)ethylene. 22. 6 0.2 43 1,3-bis(diphenylphosphino)propane. 23. 7 0. 4 44 1,4-bis(diphenylphosphino)butane... 17. 4 1. 3 45.. 1,2-bis(dipheuylph0sphino)benzene.. 14. 0 0. 6 46.. 1,2-bis(diethylphosphino)ethane 11.2 1.2

Example 47 Twenty cc. of toluene, 0.178 gram (0.5 millimole) of cobalt (III) acetyl acetonate, 0.550 gram (1 millimole) of 1,2-bis(diphenylphosphino) ethane, 1.5 cc. of ethylaluminum sesquibromide [(C H Al Br and 24 cc. of butadiene were charged to a -cc. autoclave and stirred for 2 hours at 80 C. and an ethylene pressure of 30 kg./cm. 21 grams of hexadiene-1,4 and 2.1 grams of hexadiene-2,4 were obtained. The distillation residue amounted to 1.2 grams.

Example 49 A magnetic rotary agitator-equipped ZOO-cc. autoclave was charged with 50 cc. of toluene, 1 millimole of cobalt (III) acetyl acetonate [C0(C5H|7O2)3], 1 millimole of 1,2-bis(diphenylphosphino)ethane, 47 grams of butadiene and 8 millimoles of diethylaluminum chloride. After sealing the autoclave, the reaction was carried out for 1 hour by maintaining an ethylene pressure of 50 kg./ cm. at 80-86 C. to yield 60 grams of hexadiene-1,4 and besides this 4.8 grams of hexadiene-2,4 and 11.6 grams of high boiling substances.

Example 50 Example 49 was repeated, but using ethylaluminum dichloride instead of the diethylaluminum chloride. The reaction was carried out for 1 hour at an ethylene pressure of 48 kg./cm. at 100101 C., using 60 cc. of butadiene, to yield 36.1 grams of hexadienes. Besides this, 4.4 grams of C dienes were obtained.

Example 51 When ethylaluminum sesquichloride was used as the aluminum compound component under conditions identical to those of Example 49, 11.85 grams of hexadienes were obtained. Besides this 23.9 grams of high boiling substances were formed. Of the high boiling substances, 2.5 grams were C dienes, and 3.4 grams were n-octatriene which is a dimer of butadiene.

Example 52 After charging a magnetic rotary agitator-equipped 3,405,194 13 14 autoclave with 40 cc. of toluene, 0.5 millimole of cobalt Examples 58-62 (III) acetyl acetonate and 0.5 millimole of 1,2-bis(diphenylphosphino ethane, 33.5 grams of liquified butadiene and 36 grams of liquified propylene were also charged therein, after which finally 1 cc. of triet-hylaluminum was charged to the autoclave, which was then The reactions were carried out in a 200-cc. autoclave for 2 hours (except that in the case of Example 62 the time was 18 hours) at 80 C. with an ethylene pressure of 68 kg./cm. using as catalyst 2 millimoles of ferric chloride, 1 millimole of Ph PCH CH PPh and 1 cc. of sealed. When the reaction was then carried out for 4 AlEts, but by varying the proportions of monoch1om homis at 94402 grams of.methylhexadlene we.re benzene and liquid butadiene. The results obtained are obtained. Tests confirmed that this was 2-methyl-1-c1s- Shownin Table vlbelow TABLE VI Solvent, Butadiene, Hexadiene-1,4, Other Butadiene Residue, Butadiene Example cc. g. Hexarhenes, Dimers, g. g. Conversion,

' g. Percent 80 2o. 4 24. 6 1. 6 97. 5 60 26. 8 2s. 4 1. 9 78.8 53. s 52. 0 2. 7 70. 7 20 100 68.2 7.8 55. 2 20 100 88.8 11. 3 s1. 1

4-hexadiene. Further, cyclo-dimer of butadiene was It can be seen from the results tabulated hereinabove formed as a by-product. that the use of the solvent is effective in enhancing the Example 53 selectivity for hexadiene-1,4. A reactor, as used in Example 52, was charged with 1 Example 63 millimole of cobalt (HI) acetyl acetonate, 1 millimole of When the reactlon was carried out as in Example 61, 1,2-bis(diphenylphosphino)ethane, 8.3 millimoles of diexcept that it was carried out for 16 hours at 80 C. ethylaluminum chloride. As a result of 5 hours of reacusing 1 millimole of the ferric chloride, 95.5 grams of tion at 96-100 C., 29.1 grams of Z-methyl hexadiene hexadiene-1,4 2.3 grams of hexadiene-2,4, 4.4 grams of were obtained from 26.8 grams of liquified butadiene and butadiene oligomer and 8.8 grams of residue were ob- 33 grams of liquified propylene. tamed.

Example 5 4 A magnetic agitat0r-equipped 200-cc. autoclave was charged in the presence of nitrogen with 80 cc. of toluene, 35 2 millimoles of anhydrous iron (III) chloride purified by Example 64 After charging a magnetic agitator-equipped 200-cc. autoclave with 20 cc. of toluene, 0.5 millimole (0.08 grams) of anhydrous ferric chloride, 0.5 millimole (0.19

sublimation, 20 cc. of butadiene and 1 millimole of 1,2- gram) of PIMP PPM bis(diphenylphosphino)ethane. A glass ampoule filled with 1 cc. of tn'ethylaluminum was placed gently in the autoclave. Starting with an initial pressure of ethylene 40 cm. th reaction was initiated b stirrin g gg ig g when the temperaturz becamg cc. of hqulfied butadiene and cc. of trlethylalumlnum, The reaction was Stopped after 16 hours AS a it was sealed. when the reaction was carried out for result of this reaction, 8.1 grams of hexadiene 1,4 and houzrs Y s s efhylene P to a Pressure f 1.4 grams of distillation residue were obtained. The sewhlle mamfiammg a tempeffltllre 0f 80 -90 Q, lectivity for C dienes was 85.4%. The conversion of the 45 grams of hexzfdlene:l:4 were Obtalned- Beslde thls, butadiene was 505%, of which 80% was converted to 5.4 grams of butadlene dlmers and 15.5 grams of distilla- C6 dienes tlon residue were obtalned.

Example 55 Example Example 54 was repeated except that monochloroben- 5 The procedures described in Example 64 were followed, zene was used as the solvent, the procedures described in except that 0.5 millimole of Ph PCH CH PPh was us d Examples 54 were otherwise followed. 11.8 grams of as the tertiary diphosphine and 67 grams of butadiene hexadiene-1,4 were obtained, though 1% thereof was was used, with the consequence that 100.5 grams of isomerized to hexadiene-2,4. The high boiling residue hexadiene-1,4 were obtained. The distillation residue amounted to 1.1 grams, and the selectivity for hexadiene- 55 amounted to 2.6 grams. 1,4 was 91.8%. The conversion of the butadiene was 61%, of which 88% thereof was hexadiene-1,4. EXamples 66-67 A magnetic agitator-equipped ZOO-cc. autoclave was Example 56 charged with 20 cc. of toluene, and as catalyst 2 milli- Using the catalyst of Example 54 but by adding 67 60 moles of Fecl 1 millimole of grams of the butadiene, the reaction was carried out for 5 hours at 50 C. while maintaining an ethylene pressure (CBH5)2PCH2CH2P (CB 5)2 of 70 kg./cm. 35 grams of hexadiene-1,4 were obtained. and the below-listed aluminum compounds Then, after The remainder was only 7 grams of high boiling residue. adding 120 grams of butadiene, the reactions were carried 5 out for 2 hours at C. by applying a pressure of 60 Example 57 kgjcm. with ethylene. The results tabulated below were The reaction was carried out for 18 hours at 80 C. ed. following the procedures described in Example 54, except TABLE v that 20 cc. of monochlorobenzene, 2 millimoles of ferric Alumin H 0th R chloride, 0.1 millimole of Ph PCH CH PPh and 7.3 milli- 70 Example f Butadew Compound ene-1,4, g. g. Conversion, moles of AlEt were used. As a result 51.3 grams of e ce hexadiene-1,4, 1 gram of hexadiene-2,3 and 1.3 grams of as A1(i-Bu) H 61,5 2.9 5,1 3,4 other C components were obtained. On the other hand, (1

67 AlEt c1 there were present 3.5 grams of dimers of butadiene and (10 0.). 18 9 2M 37 grams of residue in the product.

1 Example 68 Example 69 A 200-cc.autoclave was charged with 20 cc. of toluene, 1 millimol of (C H P(O)CH CH P(O)'(C H 0.5 millimole of anhydrous ferric chloride, 67 grams of liquified-butadiene and 1 cc. of AlEt After sealing the autoclave, the reaction was carried out for 1 hour at 8298 C. while maintaining a pressure of 50 kg./cm. by applying pressure to the system with ethylene. 18.4 grams of hexadienes were obtained, of which 89.2% was hexadiene-1,4.

Example 70 A 200-cc. autoclave was charged with 20 cc. of toluene, 2 millimoles of FeCl 1 millimole of cis type 67 grams of butadiene and 1 cc. of (C H Al, and sealed, following which the reaction was carried by applying pressure with ethylene. The reaction was continued for 3 hours while maintaining the ethylene pressure at 50-60 kg./cm. at 82-88 C. As a result, 64.3 grams of hexadiene-1,4 were obtained. The other products included hexadiene-1,5-hexadiene-2,4 and C dienes totaling 10.4 grams, and 17.6 grams of distillation residue. The conversion of butadiene was 97.3%.

1 6 Example 71 When Example 70 was repeated except that instead of the cis type a trans type (C H PCH=CHP(C H was used, the amount formed of hexadiene-1,4 was 40 grams. The conversion of the butadiene was 55.3%.

Example 72 A 100-cc. autoclave was charged with 0.168 gram (0.5 millimole) of iron (III) acetyl acetonate, 0.550 gram (1 millimole) of 1,2-bis(diphenylphosphino) ethane, 20 cc. of toluene and 1 cc. of diethylaluminum chloride, and the mixture was stirred for minutes at room temperature. Next, 17.4 grams of butadiene was charged to the autoclave, followed by stirring the mixture for minutes at 80 C. under an ethylene pressure of kg./cm. 22.5 grams of hexadiene-1,4 and 0.4 gram of hexadiene-2,4 were obtained. The high boiling residue amounted to 1 gram.

Example 73 A 100-cc. autoclave was charged with 10 cc. of monochlorobenzene, 0.08 g. of FeCl 1 millimole of 1,2-bis(diphenylphosphino) ethane, cc. of isoprene and 1 cc. of (C H Al, and after sealing the autoclave, the reaction was carried out for 15 hours at a temperature of 80 C. and an ethylene pressure of 40 kg./cm. The total amount of product was 10.7 grams, of which 76.5% was methyl-hexadiene-1,4 and 6.6% was methyl-hexadiene-2,4. The conversion of the isoprene was 23.7%, while the yield of the methyl-hexadiene-1,4 was 71.6%.

Example 74-82 Isoprene and ethylene were reacted, using as catalyst Coclz s s 2 2 2 e 5)2] 2.

and (C H A1 in the amounts indicated in Table VIII(a) below, whereby was obtained the results shown in Table VIII(b) below.

TABLE VIII(a) C0Cl2( PE*) z, (C2H5)3Al, Ethylene, Reaction Reaction Reaction Example Solvent, cc. g. cc. Isoprene, cc. kg./crn. Tem pgature, Tlme, hr. Mixture, g.

74 (CHzCDz, 20 0. 4634 0. 69 50 40 100 5 75 75 Xylene, 20 0. 08 1 50 40 100 5 50. 7 76 (CHzCDz, 20 0. 08 1 50 40 50 5 61 *DPE=(05111921 -CHzCHz-P(C&H5)2;

TABLE VIII(b) Activity Product, g. Isoprene Isomeri- 4Methy1- Example Conversion, Methyl-1,4- Methy1-1,4- zation 1,4-hexadiene Methyl-1,4- Methyl-2,4 C9 High percent hexadiene, hexadiene, Rate, content hexadiene hexadiene Dienes Others Boiling g./g., Co g./g., catalyst percent Substances compound 0.7 3. 4 n.d. n.d. n.d. 28. 2 0. 9 61 353 31. 1 3. 1 85. 7 29. 9 9. 2 78. 3 373 32. 9 23. 4 100 7. 5 3. G 48. 4 94. 2 8. 3 62. 3 100 16. 3 39.9 89. 3 80. 3 100 67. 9 5. 6 51 849 74. 7 7. G 81. 3 77. 6 11 88 970 85. 4 12. 4 90. 3 62 16. 4 77. 5 775 68.1 20. 9 97. 6 118 7. 3 83. 2 1, 475 129. 7 5. 8 n.d.

11.d. =not determined.

17 Examples 83-88 When butadiene is reacted with propylene using the catalysts indicated in Table IX(a) below, the results shown in Table IX(b) below, are obtained.

8. The process according to claim 1 wherein said reaction is effected at a temperature ranging between 10 and 100 C.

9. A process for preparing hexadienes which comprises TABLE IX(a) Examorganoaluminum 3rd Component, Butadiene, Propylene, Reaction Reaction ple Solvent, cc. Cobalt Compound, g. Compound, cc. g. cc cc. t Tempra- Time, hr.

ure,

83 Ethylene chloride, 20.-.. OoCl2(DPE)2, 0.08 (C2H5)3Al, 1 34 56 90-100 5 84 Toluene, 40.--. Co(acac*)3, 18 (CzH)3Al, 1 DPE, 0. 199 50 60 90-120 4 85 do do..- Co(acac*)3, 0 35.. (C2H.=,)zAlCl, 1-- D 40 55 90-100 5 Ethylene chloride, 20..-. Co(acac*) 0 18 (C2H5)3A1, 1.. 34 56 90-100 5 87. d do 00012, 0.013 (021193111, 1.. 34 56 90-100 5 88 ....do .do... Co(acac)3, 0.036... (C2H5)3A1, 1.. 34 56 90-100 5 *DPP=(CoHQzPCHzCHzCHzP(CaHs)2. T210210: (C5H702).

TABLE IX(b) Product, g. Butadiene 2.methyl-1,4- Example Conversion, hexadiene in n-Heptadiene 2-methyl-l,4- 2-methy1-1,3- Butadlene Others Residue percent Total Product,

hexadiene hexadlene Duners ercent;

We claim:

1. A process for preparing hexadienes which comprises reacting an a-monoolefin with a conjugated diolefinic hydrocarbon in the presence of a catalytic amount of a three-component catalyst comprising:

(1) a compound selected from the group consisting of (a) compound of the formula M(C5H7O2) Where M is a metal selected from cobalt and iron, and n is equal to the valence of said metal; and (b) compounds of the formula MX where X is halogen, and M and n have the meanings defined above; and (2) an organophosphorus compound selected from the group consisting of (a) compounds of the formula R PR'-),,PR where R is a member selected from alkyl and aryl, R is a member selected from alkylene, alkenylene and arylene, and n is an integer from 0 to 1; and

(b) compounds of the formula where R and R have the meanings defined above; and

(3) an organoaluminum compound of the formula R" AlZ where R" is a monovalent hydrocarbon group, Z is a member selected from hydrogen and halogen and halogens, and m is a number from 1 to 3.

2. The process according to claim 1 wherein said alpha-monoolefin is ethylene.

3. The process according to claim 1 wherein said alpha-monoolefin is propylene.

4. The process according to claim 1 wherein said conjugated diolefinic hydrocarbon is butadiene.

5. The process according to claim 1 wherein said conjugated diolefinic hydrocarbon is isoprene.

6. The process according to claim 1 wherein said components (1) and (2) are contained in a molar ratio of (2)/(1) ranging between 0.121 and 5:1.

7. The process according to claim 1 wherein said components (1) and (2) are contained in a molar ratio of (3)/(1) ranging between 0.511 and 200: 1.

where R is an alkylene group selected from the group consisting of ethylene and. 1,3-propylene[groups]; and

(b) compounds of the formula where R has the meaning defined above; and (3) a compound of the formula R AlZ where R" is an alkyl group of 1 to 4 carbon atoms; Z is a member selected from hydrogen and halogens; and m is selected from 3, 2, and 1.5; the molar ratio of said component (2) to said component (1) being in the range between 01:1 and 5:1, and the molar ratio of said component (3) to said component (1) being in the range between 0.5 :1 and 200:1.

10. The process according to claim 6 wherein a cobalt complex is prepared in advance by combining and mixing said component (1) and said component (2) in molar ratio selected from 1:1 and 1:2.

11. The process according to claim 6 wherein said catalyst composition is present in an amount wherein Co is present at the rate of 10* to 10- moles for every one mole of said conjugated diolefinic hydrocarbon.

References Cited UNITED STATES PATENTS 3,219,716 1 1/1965 Wittenberg et a1.

3,244,678 4/1966 TO0R61 26085.3 3,306,948 2/1967 Kealy 260680 3,309,418 3/1967 Hata 260-680 PAUL M. COUGHLAN, JR., Primary Examiner. 

